CN101704634A - Method for preparing conductive hollow glass microspheres - Google Patents
Method for preparing conductive hollow glass microspheres Download PDFInfo
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- CN101704634A CN101704634A CN200910185798A CN200910185798A CN101704634A CN 101704634 A CN101704634 A CN 101704634A CN 200910185798 A CN200910185798 A CN 200910185798A CN 200910185798 A CN200910185798 A CN 200910185798A CN 101704634 A CN101704634 A CN 101704634A
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Abstract
The invention relates to a method for preparing conductive hollow glass microspheres. The method comprises the following steps: (1) adding the hollow glass microspheres into cleaning liquid to be stirred and cleaned until the pH valve of the cleaning liquid is 7, and then taking the hollow glass microspheres out and drying; (2) putting the dried hollow glass microspheres in pickling solution for treatment for 1 minute, and then taking out the hollow glass microspheres for washing for 3 times until the pH valve of the washing liquid is 7; (3) putting the hollow glass microspheres into activating solution to be soaked for 2-30 minutes, and simultaneously, raising the temperature of the activating solution to 175 DEG C for thermal oxidation-reduction reaction lasting for 50 minutes; (4) putting the hollow glass microspheres into a plating bath including nickel sulfate and sodium hypophosphite for plating for 40-90 minutes, and controlling the plating temperature between 85 DEG C and 88 DEG C; and (5) taking out the hollow glass microspheres, and then washing and drying. The prepared conductive hollow glass microspheres are light in weight, high in strength, corrosion resistant and are suitable for military facilities or civil indoor and outdoor shielding materials. The method has the advantages of continuous production, low cost, superior performance and stable quality.
Description
Technical field:
The present invention relates to a kind of preparation method of hollow glass micropearl, particularly be used for the preparation method of the conductive hollow glass microspheres of application type screening of nucleus material.
Background technology:
Electromagenetic wave radiation has become the sound pollution that continues, topsoil, and water pollutes, the another big public hazards after the solid waste pollution.The main method that prevents Electromagnetic Interference at present is to use electromagnetic shielding material and electromagnetic wave absorbent material.Shielding is to isolate with the electro permanent magnetic that the conduction or the sealing surface of magnetizer carry out space, inside and outside both sides.Electromagnetic energy from from one side space to the transmission of opposite side space is suppressed to denier owing to having implemented shielding, and absorption of electromagnetic wave is to reduce electromagnetic reflected energy, thereby can convert incident electromagnetic wave to heat energy absorption of electromagnetic wave to be fallen.Material represents with effectiveness of shielding (SE) that to the degree of electromagnetic wave shielding and absorption unit is a decibel (dB), and in general, SE is big more, and then Shuai Jian degree is just high more.Electromagnetic shielding material is divided into application type and structure-type two classes, and electromagnetic screen coating is by conductive filler material, resin binder, and solvent and additive are formed.Application type screening of nucleus material is owing to have simple, the easy to use and electromagnetic parameter of technology characteristics such as adjusting easily, make its effect extremely important in screening of nucleus investigation of materials Application Areas, especially to the electromagnetic radiation protection of the stealthy performance repacking of weaponry and equipment in active service and electronics, electromagnetic compatibility etc., its effect is irreplaceable.The high-performance absorption agent is the core of application type screening of nucleus material.For satisfying the effect of microwave absorbing coating " thin, light, wide, strong ", the research of absorption agent is also developing to efficient, light weight degreeization and compoundization direction.Theoretically, metallic substance is extremely excellent hertzian wave consumable material, but anti-oxidant, the acid and alkali-resistance ability of metal fine powder; Specific inductivity is big and spectrum characteristic is poor; Density is bigger.And hollow glass micropearl is compared with metal powder, density is little, if the metalized modification is carried out on its surface, then might the substituted metal powder be used for the preparation of absorption of electromagnetic wave or electromagnetic shielding material, therefore, hollow glass micropearl surface coating material has caused extensive concern in recent years.The method for coating that occurs mainly contains physics method and chemical method, and the former mainly is a vapour deposition process; The chemistry rule mainly comprises chemical Vapor deposition process and sol-gel method etc.
Summary of the invention:
The present invention is directed to prior art and use the defective of base material and method, provide a kind of good conductivity, resistance to oxidation, low-density electro-conductive material preparation method.
A kind of preparation method of conductive hollow glass microspheres is characterized in that comprising the steps:
(1) clean hollow glass micropearl:
The configuration scavenging solution: sodium hydroxide 30～32g/L, sodium phosphate 40～45g/L, yellow soda ash 40～42g/L, tensio-active agent is an amount of,
Hollow glass micropearl adds in the scavenging solution, and after stirring, being washed till scavenging solution pH value is 7, and hollow glass micropearl is taken out oven dry;
(2) surperficial acid etching:
The pickling solution configuration: according to hydrofluoric acid and 1: 10 volume ratio of water configuration pickling solution,
Hollow glass micropearl after the oven dry is put into pickling solution handled 1 minute, take out washing 3 times, to the ph value be 7;
(3) surface active:
The preparation activation solution comprises single nickel salt and inferior sodium phosphate, and its total concn is 2.5mol/L, and wherein the mol ratio of single nickel salt and inferior sodium phosphate is 1: 4, and the pH value of activation solution is 7～7.4,
Hollow glass micropearl is put into activation solution soaked 2～30 minutes, activation solution is warming up to 175 ℃ then and carries out the thermooxidizing reduction reaction, the time length is 50 minutes;
(4) chemical plating:
The preparation of plating bath in the plating bath pond: single nickel salt 25g/L, inferior sodium phosphate 25g/L, sodium-acetate 15g/L, lactic acid 25g/L, Trisodium Citrate 5g/L, composite additive is an amount of, pH value 4.8～5.0,
Hollow glass micropearl behind the surface active is put in the plating bath pond, and plating temperature is controlled at 85～88 ℃, and the time length is 40～90 minutes,
(5) clad hollow glass micropearl is executed in taking-up, through washing, dry getting final product.
On the basis of above-mentioned basic technical scheme, further technical scheme can be arranged:
Adding polyacrylamide thickening material volume ratio in the activation solution is 1: 50; Added ammoniacal liquor in the activation solution and guaranteed the ph value, and when activation, adopted ultrasonic oscillation 7～7.4; The heap(ed) capacity of hollow glass micropearl when surperficial plating remains on 5g/L.
In the technical scheme of the present invention, hollow glass micropearl: density 0.3g/cm3～0.6g/cm3, size-grade distribution is 20 μ m～60 μ m, ultimate compression strength 10～20Mp.
Characteristics of the present invention are that equipment is simple, and are easy to operate, and covered effect is good.For the argent of main coating, copper, the chemical stability of silver is good, and preservative property are strong, good conductivity, but cost an arm and a leg; Copper with low cost, but oxidation easily, electroconductibility are also unstable, need do surface treatment.And the nickel that the present invention coats, its absorption and scattering power are all more intense, and erosion resistance is good, and cost is also cheap, is fit to suitability for industrialized production.
Compared with the prior art the present invention has following excellent results:
One, fire-retardant, high temperature resistant, can be used as the application type absorbing material, can be used for the indoor or outdoors screening of nucleus material of military or civilian;
Two, it is little to possess density, and the intensity height is compared with metal fine powder and to be possessed stronger anti-oxidant and acid and alkali-resistance ability, so can replace respective metal powder as application type screening of nucleus material;
But three continuous production are simple to operation, and compare significantly with vacuum plating and to reduce cost, and have significant industrialization prospect.
Embodiment:
The present invention will be further described below in conjunction with example, but be not limited only to this.
Embodiment one
Get hollow glass micropearl 500g, press sodium hydroxide 32g/L, sodium phosphate 45g/L, 10000 milliliters of yellow soda ash 42g/L proportional arrangement degreasing fluids are put into the back and were stirred 10 minutes, filter after washing 3 times, are 7 to get final product to the ph value, dry stand-by.
According to hydrofluoric acid and 1: 10 volume ratio of water configuration pickling solution, the hollow glass micropearl after the oven dry is put into pickling solution handled 1 minute again, take out, be put in the tank washing then 3 times with strainer filtering, to the ph value be 7.Pull out with filter screen again, dry stand-by.
The configuration activation solution, single nickel salt and inferior sodium phosphate, its total concn are 2.5mol/L, wherein the mol ratio of single nickel salt and inferior sodium phosphate is 1: 4; The pH value of activation solution is that 7～7.4. puts into activation solution with hollow glass micropearl and soaked 25～30 minutes, be warming up to 170～175 ℃ then and carry out the thermooxidizing reduction reaction, time length is 50 minutes active centers that make its surface have capacity, for final plating nickel on surface is got ready.
The hollow glass micropearl that to handle is put in the plating bath pond then, and the proportioning of plating bath is single nickel salt 25g/L in the plating bath pond, inferior sodium phosphate 25g/L, and sodium-acetate 15g/L, lactic acid 25g/L, Trisodium Citrate 5g/L, composite additive is an amount of, pH value 4.8～5.0.The temperature of plating is controlled at 85～90 ℃, and the time length is 60 minutes.The total amount of plating bath is 50L, the plating process adopts the magnetic agitation mode, because magnetic stirring apparatus is to carry out under the condition in magnetic field, microballon after the nickel plating also has magnetic, along with the easier peritrochanteric that is centered around of the microballon after the increase nickel plating of thickness of coating, this also just makes remaining microballon have that more dispersion space is easier to be contacted with plating bath, guarantees whole microballon nickel plating successes.Use distilled water wash then 3 times, and in vacuum drying oven dry fully, get final product hollow bead surface Coating Materials.
Example two
Get hollow glass micropearl 500g, press sodium hydroxide 30g/L, sodium phosphate 40g/L, 10000 milliliters of yellow soda ash 40g/L proportional arrangement degreasing fluids are put into the back and were stirred 15 minutes, filter after washing 3 times, are 7 to get final product to the ph value, dry stand-by.
According to hydrofluoric acid and 1: 10 volume ratio of water configuration pickling solution, the hollow glass micropearl after the oven dry is put into pickling solution handled 1 minute again, take out, be put in the tank washing then 3 times with strainer filtering, to the ph value be 7.Pull out with filter screen again, dry stand-by.
The configuration activation solution, single nickel salt and inferior sodium phosphate, its total concn are 2.5mol/L, wherein the mol ratio of single nickel salt and inferior sodium phosphate is 1: 4; Add the polyacrylamide thickening material, the pH value of activation solution is 7～7.4.Hollow glass micropearl is put into activation solution soaked 35～40 minutes, be warming up to 160～165 ℃ then and carry out the thermooxidizing reduction reaction, the time length is 50 minutes active centers that make its surface have capacity, for final plating nickel on surface is got ready.
The hollow glass micropearl that to handle is put in the plating bath pond then, and the proportioning of plating bath is single nickel salt 25g/L in the plating bath pond, inferior sodium phosphate 25g/L, and sodium-acetate 15g/L, lactic acid 25g/L, Trisodium Citrate 5g/L, composite additive is an amount of, pH value 4.8～5.0.The temperature of plating is controlled at 85～90 ℃, and the time length is 90 minutes.The total amount of plating bath is 50L, the plating process adopts the magnetic agitation mode, because magnetic stirring apparatus is to carry out under the condition in magnetic field, microballon after the nickel plating also has magnetic, along with the easier peritrochanteric that is centered around of the microballon after the increase nickel plating of thickness of coating, this also just makes remaining microballon have that more dispersion space is easier to be contacted with plating bath, guarantees whole microballon nickel plating successes.Use distilled water wash then 3 times, and in vacuum drying oven dry fully, get final product hollow bead surface Coating Materials.
Example three
Get hollow glass micropearl 500g, press sodium hydroxide 30g/L, sodium phosphate 40g/L, 10000 milliliters of yellow soda ash 40g/L proportional arrangement degreasing fluids are put into the back and were stirred 12 minutes, filter after washing 3 times, are 7 to get final product to the ph value, dry stand-by.
According to hydrofluoric acid and 1: 10 volume ratio of water configuration pickling solution, the hollow glass micropearl after the oven dry is put into pickling solution handled 1 minute again, take out, be put in the tank washing then 3 times with strainer filtering, to the ph value be 7.Pull out with filter screen again, dry stand-by.
The configuration activation solution, single nickel salt and inferior sodium phosphate, its total concn are 2.5mol/L, wherein the mol ratio of single nickel salt and inferior sodium phosphate is 1: 4; The pH value of activation solution is 7～7.4.Hollow glass micropearl is put into activation solution soak the employing ultrasonic oscillation, soak time is 2 minutes, be warming up to 170 ℃ then and carry out the thermooxidizing reduction reaction, the time length is 50 minutes active centers that make its surface have capacity, for final plating nickel on surface is got ready.Ultrasonic oscillation can make and produce activated state H ion in the activation solution, can impel the Ni ion to be reduced into Ni simple substance, shortens soak time.
The hollow glass micropearl that to handle is put in the plating bath pond then, the proportioning of plating bath is single nickel salt 25g/L in the plating bath pond, inferior sodium phosphate 25g/L, sodium-acetate 15g/L, lactic acid 25g/L, Trisodium Citrate 5g/L, composite additive is an amount of, the temperature of pH value 4.8～5.0. plating is controlled at 85～88 ℃, time length is 40 minutes. the total amount of plating bath is 50L, and the plating process adopts the magnetic agitation mode, because magnetic stirring apparatus is to carry out under the condition in magnetic field, microballon after the nickel plating also has magnetic, along with the easier peritrochanteric that is centered around of the microballon after the increase nickel plating of thickness of coating, this also just makes remaining microballon have that more dispersion space is easier to be contacted with plating bath, guarantees whole microballon nickel plating successes. use distilled water wash then 3 times, and in vacuum drying oven dry fully, get final product hollow bead surface Coating Materials.
Claims (4)
1. the preparation method of a conductive hollow glass microspheres is characterized in that comprising the steps:
(1) clean hollow glass micropearl:
The preparation scavenging solution: sodium hydroxide 30～32g/L, sodium phosphate 40～45g/L, yellow soda ash 40～42g/L, tensio-active agent is an amount of;
Hollow glass micropearl adds in the scavenging solution, and stirring and washing to scavenging solution pH value is 7, and hollow glass micropearl is taken out oven dry;
(2) surperficial acid etching:
Pickling solution preparation: according to hydrofluoric acid and 1: 10 volume ratio of water preparation pickling solution;
Hollow glass micropearl after the oven dry is put into pickling solution handled 1 minute, take out washing 3 times, to water lotion ph value be 7, hollow glass micropearl is pulled out drained then;
(3) surface active:
The preparation activation solution: comprise single nickel salt and inferior sodium phosphate, its total concn is 2.5mol/L, and wherein the mol ratio of single nickel salt and inferior sodium phosphate is 1: 4, and the pH value of activation solution is 7～7.4;
Hollow glass micropearl is put into activation solution soaked 2～30 minutes, activation solution is warming up to 175 ℃ then and carries out the thermooxidizing reduction reaction, the time length is 50 minutes;
(4) chemical plating:
The preparation of plating bath in the plating bath pond: single nickel salt 25g/L, inferior sodium phosphate 25g/L, sodium-acetate 15g/L, lactic acid 25g/L, Trisodium Citrate 5g/L, composite additive is an amount of, pH value 4.8～5.0;
Hollow glass micropearl behind the surface active is put in the plating bath pond, and plating temperature is controlled at 85～88 ℃, and the time length is 40～90 minutes;
(5) clad hollow glass micropearl is executed in taking-up, through washing, dry getting final product.
2. the preparation method of a kind of conductive hollow glass microspheres according to claim 1 is characterized in that adding polyacrylamide thickening material volume ratio in the activation solution is 1: 50.
3. the preparation method of a kind of conductive hollow glass microspheres according to claim 1 and 2 is characterized in that having added in the activation solution ammoniacal liquor and guarantees the ph value 7～7.4, and adopts ultrasonic oscillation in the process when activation.
4. the preparation method of a kind of conductive hollow glass microspheres according to claim 1 is characterized in that the heap(ed) capacity of hollow glass micropearl when surperficial plating remains on 5g/L.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311233A (en) * | 2011-06-02 | 2012-01-11 | 中国科学院理化技术研究所 | Surface chemical plating treatment process for hollow glass microsphere, plated metal hollow glass microsphere and application thereof |
| CN102557480A (en) * | 2011-12-11 | 2012-07-11 | 太原海祥源科技有限公司 | Preparation method of nickel plating glass micro-bead for conductive compound |
| CN103578650A (en) * | 2012-08-10 | 2014-02-12 | 贵州省冶金化工研究所 | Method for preparing core-shell type conductive hollow glass beads |
| CN103601387A (en) * | 2013-11-18 | 2014-02-26 | 天津大学 | Method of preparing heat insulating material by modifying surfaces of hollow glass beads |
| CN103823265A (en) * | 2014-03-04 | 2014-05-28 | 四川中科倍特尔技术有限公司 | Full-aluminizing high-refractive-index glass microbead as well as production process thereof |
| CN106928678A (en) * | 2015-12-30 | 2017-07-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of lightweight electromagnetic shielding makrolon material and preparation method thereof |
| CN109183010A (en) * | 2018-11-01 | 2019-01-11 | 中钢集团马鞍山矿院新材料科技有限公司 | Hollow glass micropearl roughing in surface-nickel plating method |
| CN111218041A (en) * | 2020-03-14 | 2020-06-02 | 温州市瓯海凯欣鞋业有限公司 | Wear-resistant sole material and manufacturing method thereof |
| CN113929312A (en) * | 2021-09-16 | 2022-01-14 | 武汉软件工程职业学院 | Method for plating nickel on glass surface without activation of noble metal |
-
2009
- 2009-11-30 CN CN200910185798A patent/CN101704634A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311233A (en) * | 2011-06-02 | 2012-01-11 | 中国科学院理化技术研究所 | Surface chemical plating treatment process for hollow glass microsphere, plated metal hollow glass microsphere and application thereof |
| CN102557480A (en) * | 2011-12-11 | 2012-07-11 | 太原海祥源科技有限公司 | Preparation method of nickel plating glass micro-bead for conductive compound |
| CN102557480B (en) * | 2011-12-11 | 2015-11-18 | 太原海祥源科技有限公司 | A kind of preparation method of nickel plating glass micro-bead for conductive compound |
| CN103578650A (en) * | 2012-08-10 | 2014-02-12 | 贵州省冶金化工研究所 | Method for preparing core-shell type conductive hollow glass beads |
| CN103601387A (en) * | 2013-11-18 | 2014-02-26 | 天津大学 | Method of preparing heat insulating material by modifying surfaces of hollow glass beads |
| CN103601387B (en) * | 2013-11-18 | 2015-07-22 | 天津大学 | Method of preparing heat insulating material by modifying surfaces of hollow glass beads |
| CN103823265A (en) * | 2014-03-04 | 2014-05-28 | 四川中科倍特尔技术有限公司 | Full-aluminizing high-refractive-index glass microbead as well as production process thereof |
| CN106928678A (en) * | 2015-12-30 | 2017-07-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of lightweight electromagnetic shielding makrolon material and preparation method thereof |
| CN109183010A (en) * | 2018-11-01 | 2019-01-11 | 中钢集团马鞍山矿院新材料科技有限公司 | Hollow glass micropearl roughing in surface-nickel plating method |
| CN109183010B (en) * | 2018-11-01 | 2020-11-10 | 中钢集团马鞍山矿院新材料科技有限公司 | Method for roughening surface of hollow glass bead and plating nickel |
| CN111218041A (en) * | 2020-03-14 | 2020-06-02 | 温州市瓯海凯欣鞋业有限公司 | Wear-resistant sole material and manufacturing method thereof |
| CN113929312A (en) * | 2021-09-16 | 2022-01-14 | 武汉软件工程职业学院 | Method for plating nickel on glass surface without activation of noble metal |
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Application publication date: 20100512 |